CN-122013012-A - Amorphous alloy structure regulator, magnesium-based composite material and soluble bridge plug as reinforcing phases thereof

CN122013012ACN 122013012 ACN122013012 ACN 122013012ACN-122013012-A

Abstract

The invention belongs to the technical field of composite materials, and particularly relates to an amorphous alloy tissue regulator, a magnesium-based composite material taking the amorphous alloy tissue regulator as a reinforcing phase and a preparation method of the magnesium-based composite material, wherein in the preparation method, a core is that a magnesium-based amorphous alloy is divided into two parts, one part of the surface of the magnesium-based amorphous alloy is coated with a zirconia protective layer, and the other part of the magnesium-based amorphous alloy is in an uncoated state; the two materials are sequentially introduced into the magnesium alloy matrix according to the proportion, and the cooperative design and accurate matching of the mechanical property and the corrosion rate of the materials can be realized by regulating and controlling the proportion of coated amorphous and uncoated amorphous. Meanwhile, the magnesium-based composite material synchronously solves the key problems of low strength and difficult regulation and control of degradation rate of the traditional degradable magnesium alloy, and realizes the integrated regulation and control of strength-plasticity-degradation performance. In addition, the prepared magnesium-based composite material lays a key material foundation for manufacturing a high-performance controllably-degradable magnesium-based structural member, and has important significance for promoting efficient development of shale oil gas.

Inventors

LIU BAOSHENG
SONG SHIJIE
ZHANG YUEZHONG
ZHANG XIAORU
LIU ZEXUE

Assignees

太原科技大学
山西八达镁业有限公司

Dates

Publication Date: 20260512
Application Date: 20260112

Claims (10)

1. The preparation method of the amorphous alloy tissue regulator is characterized by comprising the following steps: S11, preparing micron-sized magnesium-based amorphous alloy powder, wherein the magnesium-based amorphous alloy is MgCuYZn amorphous alloy, and the atomic percentage composition of the magnesium-based amorphous alloy powder is Mg a Cu b Y c Zn d , wherein the atomic percentage composition of a, b, c, d is a+b+c+d= 100,40, a is more than or equal to 70,20, b is more than or equal to 40, c is more than or equal to 1, and is more than or equal to 20, and d is more than or equal to 1 and is less than or equal to 20; S12, preprocessing the magnesium-based amorphous alloy powder; S13, depositing a zirconia coating on the surface of the magnesium-based amorphous alloy powder by adopting an atomic layer deposition system to obtain magnesium-based amorphous alloy powder coated with the zirconia coating on the surface; the thickness of the zirconia coating is 10-30 nm.
2. The method for preparing the amorphous alloy structure modulator according to claim 1, wherein the specific process for preparing the micron-sized magnesium-based amorphous alloy powder in the step S11 comprises the following steps: And ball-milling MgCuYZn amorphous alloy strips for 1-3 hours at a rotating speed of 150-250 rpm to obtain MgCuYZn amorphous alloy powder with a particle size of 10-25 mu m, wherein zirconia balls are used as ball milling media in ball milling, the ratio of the zirconia balls to the MgCuYZn amorphous alloy strips is 20-40:1, and absolute ethyl alcohol with the weight of 1-5% is added as a grinding aid in the ball milling process, and ball milling is carried out in a vacuum environment.
3. The method for preparing the amorphous alloy structure modulator according to claim 1, wherein the specific process of pretreating the magnesium-based amorphous alloy powder in step S12 comprises: Placing MgCuYZn amorphous alloy powder into a centrifuge tube, adding acetone, processing for 30min under ultrasonic conditions, centrifuging and discarding supernatant, adding absolute ethyl alcohol, processing for 30min under ultrasonic conditions, centrifuging and discarding supernatant, and drying the cleaned amorphous alloy powder in a vacuum drying oven at 60 ℃ for 2h; Wherein the ultrasonic conditions are that the ultrasonic frequency is 80kHz, the power density is 0.8W/cm 2 , and the time is 1min.
4. The method for preparing the amorphous alloy structure modulator according to claim 1, wherein in step S13, a zirconia coating is deposited on the surface of the magnesium-based amorphous alloy powder by using an atomic layer deposition system, and the specific operation steps of obtaining the magnesium-based amorphous alloy powder with the zirconia coating coated on the surface are as follows: spreading the pretreated MgCuYZn amorphous alloy powder in a sample boat, loading the sample boat into a constant temperature area of a reaction chamber of an atomic layer deposition system, vacuumizing, starting a sample table vibration device and deposition operation after the treatment, running 200 ALD cycles for deposition, cooling the reaction chamber to below 80 ℃ under continuous N 2 flow after the deposition is finished, obtaining MgCuYZn amorphous alloy powder with a zirconia coating deposited on the surface, heating the MgCuYZn amorphous alloy powder with the zirconia coating deposited to 250 ℃ at 2 ℃ per min under the protection of N 2 , preserving heat for 1h for annealing, and dry-grinding at 100rpm for 5min after the annealing treatment to obtain magnesium-based amorphous alloy powder with the zirconia coating coated on the surface.
5. The method for preparing an amorphous alloy texture regulator according to claim 4, wherein, the atomic layer deposition system comprises the following materials, cleaning, parameter setting and ALD cycle deposition operations: preparing material MgCuYZn amorphous alloy powder, tetra (dimethylamino) zirconium and deionized water; Firstly heating an ALD reaction chamber to 200 ℃, introducing nitrogen to purge for 30min, then carrying out O 2 plasma treatment for 10min under the condition of 100W power for cleaning an atomic layer deposition system, secondly setting the temperature of the ALD reaction chamber to 160 ℃, the temperature of a tetra (dimethylamino) zirconium source bottle to 75 ℃, the temperature of a gas pipeline to 100 ℃, the temperature of a deionized water source bottle to 25 ℃, pumping the basic vacuum degree of the atomic layer deposition system to be less than 1.0X10 -4 Torr, stabilizing the working pressure at 1.0Torr by introducing N 2 , setting the frequency of a vibration device to be 30Hz and the amplitude to be 2mm, and finally carrying out 200 ALD cycles for deposition, wherein the operation steps of one complete ALD cycle are as follows: a tetra (dimethylamino) zirconium pulse, namely introducing tetra (dimethylamino) zirconium steam into an ALD reaction chamber, wherein the pulse time is 1s; purging with high-purity N 2 for 40s; Deionized water pulse, namely introducing steam into the ALD reaction chamber for 1s; and purging with N 2 for 40s after the second purging with N 2 .
6. A method for preparing a magnesium-based composite material, which is characterized in that the amorphous alloy structure regulator of claim 5 is used as a reinforcing phase, and Mg-6Al is used as a matrix to prepare the magnesium-based composite material, and the preparation steps are as follows: S21, smelting basal magnesium to obtain magnesium-based melt, and stirring and adding preheated pure aluminum, uncoated amorphous alloy powder and amorphous alloy structure regulator into the magnesium-based melt to obtain alloy melt; S22, pouring and cooling the alloy melt to form the magnesium-based composite material.
7. The method for preparing the magnesium-based composite material according to claim 6, wherein the step S21 is characterized in that the magnesium-based melt is obtained by smelting basal magnesium, the preheated pure aluminum, the uncoated amorphous alloy powder and the amorphous alloy structure regulator are added into the magnesium-based melt under stirring to obtain an alloy melt, the specific steps are that commercial pure magnesium with the purity of not lower than 99.95% is placed into a crucible resistance furnace, the commercial pure magnesium is gradually heated to 720 ℃ under the mixed protective gas atmosphere with the volume fraction ratio of CO 2 to SF 6 of 99:1 and is kept at the temperature of being completely melted, the commercial pure aluminum with the purity of not lower than 99.90% is added into the magnesium-based melt at the temperature of 720 ℃ and is kept at the temperature of 20min, the preheated uncoated amorphous alloy powder is added and is kept at the temperature of 10min, and finally the preheated amorphous alloy structure regulator is added and kept at the temperature of 5min when the temperature is gradually lowered and stabilized at 670 ℃, and the alloy melt is finally obtained; the preheating treatment is that 1h is preheated at 200 ℃, the whole adding process of the step S21 is carried out in ultrasonic stirring, the ultrasonic power is 600-1000W, the alloy melt is poured and cooled to be molded in the step S22, and the specific steps of obtaining the magnesium-based composite material comprise the steps of immediately pouring the alloy melt after stirring and heat preservation into a metal mold to realize rapid solidification, and obtaining the magnesium-based composite material.
8. The magnesium-based composite material is characterized by being obtained by a preparation method of the magnesium-based composite material according to any one of claims 6-7, wherein the chemical composition of the magnesium-based composite material is Mg-6Al-4MgCuYZn, the content of an amorphous alloy tissue regulator is 4wt%, the content of pure aluminum is 6wt%, the content of pure magnesium is 90wt%, and meanwhile, the mass percentage of amorphous alloy powder with a ZrO 2 coating coated on the surface in MgCuYZn of 4wt% and uncoated amorphous alloy powder is 7-9:3-1.
9. The magnesium-based composite material according to claim 8, wherein the magnesium-based composite material has an ultimate tensile strength, elongation and corrosion rate of 260MPa, 9.8% and 254mm/year, respectively, when the mass percentage of the amorphous alloy powder surface-coated with ZrO 2 coating in 4wt% MgCuYZn to the uncoated amorphous alloy powder is 9:1.
10. A soluble bridge plug comprising a bridge plug body and a sealing structure, an anchoring structure and an drift diameter structure disposed on the bridge plug body, wherein the bridge plug body is made in whole or in part of the magnesium-based composite material of any one of claims 8-9.

Description

Amorphous alloy structure regulator, magnesium-based composite material and soluble bridge plug as reinforcing phases thereof Technical Field The invention belongs to the technical field of composite materials, and particularly relates to an amorphous alloy tissue regulator, a magnesium-based composite material serving as a reinforcing phase and a soluble bridge plug. Background The magnesium alloy is used as the metal structural material with the lightest weight potential, has high specific strength, excellent damping performance and good recoverability, and has wide application in the fields of aerospace, transportation and the like. In recent years, along with the rapid development of unconventional energy exploitation of shale oil gas and the like, the application of magnesium alloy in a soluble temporary plugging tool is highly valued. By utilizing the characteristic of automatic dissolution in the underground environment, tools such as bridge plugs and the like can be automatically dissolved after fracturing operation without drilling operation, thereby remarkably improving the exploitation efficiency, reducing the environmental impact and conforming to the development direction of the green exploitation technology. However, the high chemical activity of the magnesium alloy causes that the corrosion rate of the magnesium alloy in the underground environment containing Cl - is difficult to control stably, unpredictable excessively fast or excessively slow corrosion is easily generated due to the influence of fluctuation of working conditions, meanwhile, the strength of the existing commercial magnesium alloy is generally low, and the requirement of the high-pressure working condition on the pressure-bearing performance of the soluble bridge plug is difficult to meet. The bottleneck problem of the insufficient strength and uncontrollable corrosion rate seriously restricts the large-scale application of the magnesium alloy in the soluble bridge plug. The amorphous alloy powder is used as a novel material with a long-range disordered structure, and has high strength, high hardness and excellent corrosion resistance. Researches show that the mechanical property and corrosion stability of the material can be synchronously improved through load transmission strengthening and microstructure regulation and control by introducing a proper amount of amorphous alloy powder into a magnesium matrix as a reinforcing phase. Therefore, development of a novel magnesium-based composite material based on amorphous alloy powder reinforcement is needed, the technical bottleneck of the existing soluble magnesium alloy in the aspects of strength and corrosion control is hopeful to be broken through, a more reliable material solution is provided for shale oil gas efficient development, and important scientific research value and engineering application prospect are provided. Disclosure of Invention In view of the above, a first object of the present invention is to provide an amorphous alloy structure controlling agent and a preparation method thereof, which aims to realize the cooperative control of the mechanical properties and corrosion rate of a composite material by introducing amorphous alloy powder coated with a ZrO 2 coating on the surface into a magnesium alloy. A second object of the present invention is to provide a method for preparing a magnesium-based composite material using an amorphous alloy structure controlling agent as a reinforcing phase. The amorphous alloy powder with different ZrO 2 coating ratios is compared to enhance the influence on the comprehensive performance of the magnesium-based composite material, so that the bottleneck problem that the strength of the traditional magnesium alloy is insufficient and the corrosion rate is difficult to regulate and control simultaneously is solved, and the cooperative regulation and control on the strength, plasticity and corrosion resistance of the magnesium alloy are realized. A third object of the present invention is to provide a soluble bridge plug prepared based on the magnesium-based composite material described above. In order to achieve the aim of the invention, the invention adopts the following technical scheme: in a first aspect, the present invention provides a method for preparing an amorphous alloy structure modulator, comprising the steps of: S11, preparing micron-sized magnesium-based amorphous alloy powder, wherein the magnesium-based amorphous alloy is MgCuYZn amorphous alloy, and the atomic percentage composition of the magnesium-based amorphous alloy powder is Mg aCubYcZnd, wherein the atomic percentage composition of a, b, c, d is a+b+c+d= 100,40, a is more than or equal to 70,20, b is more than or equal to 40, c is more than or equal to 1, and is more than or equal to 20, and d is more than or equal to 1 and is less than or equal to 20; S12, preprocessing the magnesium-based amorphous alloy powder; S13, depositing a zirconia coating on t